US4073757A - Hardenable, boron-containing reinforcing resins for rubber - Google Patents

Hardenable, boron-containing reinforcing resins for rubber Download PDF

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Publication number
US4073757A
US4073757A US05/749,456 US74945676A US4073757A US 4073757 A US4073757 A US 4073757A US 74945676 A US74945676 A US 74945676A US 4073757 A US4073757 A US 4073757A
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weight
boron
parts
reaction
rubber
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US05/749,456
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English (en)
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Manfred Schmidt
Dieter Freitag
Hermann Fries
Erich Esch
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • modified synthetic resins such as these produce an undesirable increase in viscosity and, for this reason, adversely affect further processibility. Hitherto they have been used as hardeners in nitrile rubber (NBR) only, producing no hardening effect in other rubber materials.
  • NBR nitrile rubber
  • novolaks by condensing diphenylol propane (bisphenol A) with formalin in the presence of an organic solvent is known from DT-OS 1,570,351.
  • Products of this kind are not suitable for use as reinforcing resins for rubbers because, when hardened in the presence of a formaldehyde donor such as hexamethylene tetramine, for example, novolak-rubber mixtures of the kind in question adhere to a considerable extent to the mixing and calender rolls.
  • thermosetting boron-containing synthetic resins produced by condensing mixed boric acid esters of phenols, diphenylol propane and alcohols with paraformaldehyde.
  • NBR n-butadiene rubber
  • formaldehyde donor such as hexamethylene tetramine
  • resins obtained by the partial transesterification of a diphenylol alkane novolak with boric acid alkyl esters, optionally formed in situ, and partial reaction with an unsaturated fatty acid or esters thereof have excellent properties as reinforcing resins and may be used in rubbers.
  • a formaldehyde donor such as hexamethylene tetramine for example
  • the addition of 10% by weight of a resin according to the invention to SBR gives a degree of hardness equivalent to that obtained by adding 45% by weight of a standard commercial grade low molecular weight styrene polymer hardener to SBR.
  • the SBR-based rubber mouldings hardened by the resins according to the invention are distinguished by the outstanding resistance of their hardness properties to high temperature, unlike SBR-based rubber mouldings hardened by a standard commercialgrade thermoplastic reinforcing agent, such as low molecular weight polystyrene.
  • the present invention relates to a process for the production of hardenable, boron-containing reinforcing resins for rubber by reacting diphenylol alkane novolaks with boron compounds and unsaturated fatty acids or fatty acid esters, distinguished by the fact that diphenylol alkane novolaks with an average molecular weight (osmotically determined) Mos of from 400 to 1600, preferably from 600 to 1200, are reacted with from 20 to 100 parts by weight of a boric acid trialkyl ester containing from 1 to 4 carbon atoms per alkyl chain or with from 18 to 90 parts by weight of boric acid or with from 10 to 50 parts by weight, preferably from 15 to 20 parts by weight, of boron trioxide in the presence of a C 1 -C 4 -alcohol, after which the boric acid ester resins obtained are reacted at elevated temperatures with from 15 to 35 parts by weight of an unsaturated fatty acid or esters thereof.
  • the invention also relates to the boron-containing resins obtainable by the process described above which are soluble in methanol, ethanol, propanol, isopropanol, butanol, isobutanol, dioxane, tetrahydrofuran, acetone, methylethyl ketone, ethyl acetate, butyl acetate, methyl and ethylene glycol acetate, and have an iodine number of from 80 to 200, preferably from 110 to 170, an OH-number of from 200 to 500, preferably from 240 to 450, and a boron content of up to 7% by weight, preferably from 1.5 to 5% by weight.
  • the diphenylol alkane novolak corresponds to the following formula: ##STR1## in which: m, n have values between 1 and 2, with the proviso that m+n ⁇ 2,
  • R represents C 1 -C 4 -alkyl, such as methyl, ethyl, propyl or butyl,
  • R 1 represents R or X
  • X represents a novolak which is obtained by the condensation of an aldehyde with a diphenylol alkane or with a mixture of diphenylol alkanes and hydroxy (phenyl hydroxy) indanes in the presence of acid catalysts and which contains free phenolic OH-groups.
  • R' h or R
  • R and R' C 4 -C 7 -alkylene, in addition to which R and R' may form a carbocyclic ring with the carbon atom by which they are joined, and
  • R" h or C 1 -C 4 -alkyl.
  • bisphenol A or a mixture of bisphenol A isomers with hydroxy phenyl hydroxy indanes corresponding to the general formula (III), the ratio by weight of the bisphenol A isomers to the hydroxy phenyl hydroxy indanes of the general formula (III) amounting to between 4:1 and 9:1 and preferably to between 6:1 and 8:1.
  • the diphenylol alkane or diphenylol alkane mixture is reacted with from 100 to 140 mole % and preferably with from 120 to 130 mole % of an aldehyde in the presence of from 40 to 150 parts by weight and preferably in the presence of from 60 to 80 parts by weight of an organic solvent (based on 100 parts by weight of the diphenylol alkane), such as for example benzene, toluene, xylene, ethyl acetate, butylacetate, methyl glycol or ethylene glycol acetate and in the presence of from 0.01 to 1 mole %, preferably 0.5 mole %, of an acidic organic or inorganic catalyst or mixtures thereof, the reaction being carried out at boiling temperature in known manner.
  • the reaction time amounts to between about 20 minutes and 2 hours and preferably to between 30 minutes and 1 hour.
  • Chloral, furfurol, propionaldehyde, butyraldehyde, acetaldehyde and formaldehyde may be used as aldehydes. It is preferred to use aqueous formalin solution, trioxane or paraformaldehyde.
  • the acid catalysts used are solid and liquid organic acids, such as oxalic acid, succinic acid, acetic acid and lactic acid.
  • Inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid and combinations of the above-mentioned organic and inorganic acids may also be used. Oxalic acid and phosphoric acid are preferably used.
  • Boric acid alkyl esters are compounds corresponding to the formula B(OR) 3 , in which R represents an alkyl radical with from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl.
  • R represents an alkyl radical with from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl.
  • the ester used for the reaction is usually formed in situ from the corresponding alcohol and boron trioxide or boric acid. It is, of course, also possible to use separately synthesised boric acid esters.
  • Suitable unsaturated fatty acids or their esters are compounds with from 24 to 41 carbon atoms in the acid moiety and, in the case of the ester, with from 1 to 4 carbon atoms, in the alkyl chain of the alcohol moiety.
  • Monoglycerides, diglycerides or triglycerides may also be used.
  • Linseed oil fatty acid soya oil fatty acid, tall oil fatty acid, peanut oil fatty acid, commercial-grade conjugated unsaturated fatty acids, such as conjuene fatty acid, ricinoleic acid, ricinene fatty acid or mixtures thereof, and also their glycerides or glyceride mixtures or their methyl esters or methyl ester mixtures.
  • linseed oil fatty acid soya oil fatty acid, conjuene fatty acid and castor oil.
  • the unsaturated fatty acids or their esters preferably have iodine numbers above 40.
  • the diphenylol alkane novolak is diluted in 40 to 120 parts by weight, preferably 60 to 100 parts by weight (based on 100 parts by weight of diphenylol alkane) of an alcohol ROH, in which R is a straight-chain or branched alkyl group with from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or t-butyl, preferably ethyl. It is, of course, also possible to use the novolak solution or novolak suspension left behind after the azeotropic distillation of water in the production of the novolak.
  • the boric acid ester is reacted with 15 to 35 parts by weight and preferably with 20 to 27 parts by weight (based on 100 parts by weight of the diphenylol alkane) of the unsaturated fatty acid or its ester for 10 to 60 minutes and preferably for 15 to 30 minutes at a bath temperature of from 100° to 200° C, preferably from 130° to 170° C.
  • the solution formed during the production of the above boric acid ester may, of course, also be used. In this case, approximately 80% by weight of the total quantity of solvent has to be distilled off.
  • the residual solvent and monomeric reaction products are distilled off first under normal pressure and then in a water jet vacuum.
  • the resin is run off from the reaction vessel in liquid form and is ground after solidification.
  • both the reaction steps and also the component reaction steps described may be carried out at the same time providing all the reactants are simultaneously introduced accordingly.
  • fatty acids or their esters to the diphenylol alkane novolak together with the boric acid alkyl esters, boric acid or boron trioxide.
  • the resins according to the invention are incorporated in the presence of a formaldehyde donor, such as for example hexamethylene tetramine, paraformaldehyde, trioxy or tetraoxy methylene, on the mixing units normally used for processing rubber, such as for example rolls, kneaders and high speed mixers.
  • a formaldehyde donor such as for example hexamethylene tetramine, paraformaldehyde, trioxy or tetraoxy methylene
  • the resins according to the invention are incorporated at temperatures in the range of from 70° to 120° C and preferably at temperatures in the range of from 80° to 100° C.
  • Natural rubber styrene-butadiene rubber, chloroprene rubber, nitrile rubber, isoprene rubber, butadiene rubber, EPDM, butyl rubber and transpolypentenamer rubber.
  • the usual fillers such as active silicas, carbon black, kaolin, chalk, and also antiagers, crosslinking chemicals, vulcanisation accelerators and other standard additives, may be added to the rubbers.
  • the resins according to the invention are added to the rubbers in quantities sufficient to produce a reinforcing effect, preferably in quantities of from 5 to 10 parts by weight and with particular preference in quantities of from 10 to 60 parts by weight, based on 100 parts by weight of rubber.
  • the rubber mixtures thus produced may be processed by the usual techniques, for example moulding, extrusion or calendering, to form shaped articles such as, for example, soles, rollers, floor coverings and sealing rings.
  • Vulcanisation is carried out by the usual processes, for example in presses, in steam, in hot air tunnels or in salt baths, at temperatures in the range of from about 130° to 210° C.
  • a resin is prepared with the same starting materials, the same quantities and under the same reaction conditions as in Example 1, except that, instead of 300 g of castor oil, the same quantity by weight of a commercial grade conjugated unsaturated fatty acid (Konjuvandol fatty acid, a product of Unichema) is used.
  • a commercial grade conjugated unsaturated fatty acid Konjuvandol fatty acid, a product of Unichema
  • Working up in the same way as in Example 1 gives 1.8 kg of a resin having a softening point of 74° C.
  • Example 2 Following the procedure described in Example 1, the hardener resin obtained in accordance with Example 2 is worked into SBR and tested in comparison with a standard styrene-butadiene resin (containing approximately 85% of styrene).
  • the "primary resin" obtained during the production of bisphenol A a mixture of bisphenol A isomers with hydroxy phenyl hydroxy indane and hydroxy phenyl hydroxy chromane isomers in a ratio by weight of approximately 7:1:1, is used for this Example.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
US05/749,456 1975-12-20 1976-12-10 Hardenable, boron-containing reinforcing resins for rubber Expired - Lifetime US4073757A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2557613A DE2557613C2 (de) 1975-12-20 1975-12-20 Härtbares, borhaltiges Harz und dessen Verwendung als Verstärkerharz für natürlichen und/oder synthetischen Kautschuk
DT2557613 1975-12-20

Publications (1)

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US4073757A true US4073757A (en) 1978-02-14

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US (1) US4073757A (de)
JP (2) JPS5811892B2 (de)
CA (1) CA1066448A (de)
DE (1) DE2557613C2 (de)
FR (1) FR2335539A1 (de)
GB (1) GB1515068A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182697A (en) * 1978-02-08 1980-01-08 Bayer Aktiengesellschaft Process for the preparation of boron-containing phenol-formaldehyde resins
US4232134A (en) * 1978-11-11 1980-11-04 Bayer Aktiengesellschaft Process for isolating boron-containing phenol/formaldehyde resins
CN101798436A (zh) * 2010-03-12 2010-08-11 江苏大学 硼、亚麻油双改性酚醛树脂基摩阻复合材料及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2934936A1 (de) * 1979-08-29 1981-03-19 Bayer Ag, 5090 Leverkusen Wickelreifen
JP6713173B2 (ja) * 2018-06-04 2020-06-24 株式会社シキシマ 冷却装置
CN116376178A (zh) * 2023-04-21 2023-07-04 保定三源橡胶有限公司 一种隔热抗烧高耐热输送带用胶料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2022827A (en) * 1935-12-03 Samuel ruben
US3117153A (en) * 1960-03-16 1964-01-07 Exxon Research Engineering Co Preparation of higher boron compounds and alcohol derivatives thereor
US3189567A (en) * 1959-07-17 1965-06-15 Albert Ag Chem Werke Process for vulcanization of butyl rubber
US3384586A (en) * 1966-03-17 1968-05-21 Lubrizol Corp Resinous compositions
US3455851A (en) * 1965-02-27 1969-07-15 Distillers Co Yeast Ltd Rubber reinforcing compositions comprising phenol/sulfur resins

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
DE474561C (de) * 1925-02-26 1929-04-10 Chemische Fabriken Dr Kurt Alb Verfahren zur Herstellung von esterartigen Derivaten der Kondensationsprodukte aus Phenolen und Carbonylverbindungen
DE537367C (de) * 1928-12-14 1931-11-02 Erich Asser Dr Verfahren zur Erhoehung des Schmelzpunktes von Novolaken und den daraus mit natuerlichen Harzsaeuren bereiteten oelloeslichen Verbindungen
US2064950A (en) * 1934-08-11 1936-12-22 Rosenblum Israel Resinous condensation product and method of producing same
GB613073A (en) * 1946-04-24 1948-11-22 Semtex Ltd Improvements in or relating to moulding compositions and to moulded articles made therefrom
FR1017523A (fr) * 1949-03-10 1952-12-11 Gen Mills Inc Perfectionnements relatifs aux esters d'une résine de phénol-formaldéhyde et à leur procédé de préparation
US3487045A (en) * 1964-11-30 1969-12-30 Hooker Chemical Corp Aromatic polymers which are prepared by reacting an ortho phenolic novolak with boron compounds
DE1570396A1 (de) * 1965-10-20 1969-07-24 Albert Ag Chem Werke Verfahren zur Herstellung von acetylgruppen-und katalysatorfreien Esterharzen aus Polyphenolen,insbesondere Phenolnovolaken,und Carbonsaeuren

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2022827A (en) * 1935-12-03 Samuel ruben
US3189567A (en) * 1959-07-17 1965-06-15 Albert Ag Chem Werke Process for vulcanization of butyl rubber
US3117153A (en) * 1960-03-16 1964-01-07 Exxon Research Engineering Co Preparation of higher boron compounds and alcohol derivatives thereor
US3455851A (en) * 1965-02-27 1969-07-15 Distillers Co Yeast Ltd Rubber reinforcing compositions comprising phenol/sulfur resins
US3384586A (en) * 1966-03-17 1968-05-21 Lubrizol Corp Resinous compositions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, vol. 81, No. 10, Sep. 9, 1974, p. 50472y. *
Chemical Abstracts, vol. 83, No. 10, Sep. 8, 1975, p. 80240e. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182697A (en) * 1978-02-08 1980-01-08 Bayer Aktiengesellschaft Process for the preparation of boron-containing phenol-formaldehyde resins
US4232134A (en) * 1978-11-11 1980-11-04 Bayer Aktiengesellschaft Process for isolating boron-containing phenol/formaldehyde resins
CN101798436A (zh) * 2010-03-12 2010-08-11 江苏大学 硼、亚麻油双改性酚醛树脂基摩阻复合材料及其制备方法
CN101798436B (zh) * 2010-03-12 2012-06-20 江苏大学 硼、亚麻油双改性酚醛树脂基摩阻复合材料及其制备方法

Also Published As

Publication number Publication date
JPS5811892B2 (ja) 1983-03-05
GB1515068A (en) 1978-06-21
JPS5874712A (ja) 1983-05-06
FR2335539A1 (fr) 1977-07-15
FR2335539B1 (de) 1980-07-18
DE2557613C2 (de) 1984-04-26
JPS5277195A (en) 1977-06-29
DE2557613A1 (de) 1977-06-30
CA1066448A (en) 1979-11-13

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